Active substance combinations having insecticidal and acaricdal properties

ABSTRACT

The invention relates to insecticidal mixtures for protecting plants against attack by pests comprising  
     (a) compounds of the formula (I)  
                 
 
     in which W, X, Y, Z, A, B, D and G are each as defined in the disclosure, and  
     (b) specified agonists or antagonists of nicotinic acetylcholine receptors

[0001] The present invention relates to novel active compoundcombinations comprising known cyclic ketoenols on the one hand and otherknown insecticidally active compounds on the other hand, whichcombinations are highly suitable for controlling animal pests such asinsects and undesired acarides.

[0002] It is already known that certain cyclic ketoenols haveherbicidal, insecticidal and acaricidal properties. The activity ofthese substances is good; however, at low application rates it issometimes unsatisfactory.

[0003] Unsubstituted bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599 and EP-A-415 211) and substituted monocyclic3-aryl-pyrrolidine-2,4dione derivatives (EP-A-377 893 and EP-A442 077)with herbicidal, insecticidal or acalicidal action are known.

[0004] Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives(EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063,EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO97/01 535, WO 97/02 243,. WO 97/36 868, WO 97/ 43 275, WO 98/05 638, WO98/06 721, WO 98/25 928, WO 99/16 748, WO 99/24 437, WO 99/43 649, WO99/48 869 and WO 99/55 673).

[0005] Furthermore, it is already known that numerous heterocycles,organotin compounds, benzoylureas and pyrethroids have insecticidal andacaricidal properties (cf. WO 93/22 297, WO 93/10083, DE-A-2 641 343,EP-A-347 488, EP-A-210 487, U.S. Pat. No. 3,364,177 and EP-A-234 045).However, the activity of these substances is not always satisfactory.

[0006] It has now been found that mixtures of compounds of the formula(I)

[0007] in which

[0008] X represents halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy or cyano,

[0009] W, Y and Z independently of one another each represent hydrogen,halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or cyano,

[0010] A represents hydrogen, in each case optionallyhalogen-substituted alkyl, alkoxyalkyl, saturated, optionallysubstituted cycloalkyl, in which optionally at least one ring atom isreplaced by a heteroatom,

[0011] B represents hydrogen or alkyl,

[0012] A and B together with the carbon atom to which they are attachedrepresent a saturated or unsaturated unsubstituted or substituted cyclewhich optionally contains at least one heteroatom,

[0013] D represents hydrogen or an optionally substituted radicalselected from the group consisting of alkyl, alkenyl, alkoxyalkyl,saturated cycloalkyl in which optionally one or more ring members arereplaced by heteroatoms,

[0014] A and D together with the atoms to which they are attachedrepresent a saturated or unsaturated cycle which is unsubstituted orsubstituted in the A,D moiety and optionally contains at least oneheteroatom,

[0015] G represents hydrogen (a) or represents one of the groups

[0016] in which

[0017] E represents a metal ion or an ammonium ion,

[0018] L represents oxygen or sulphur,

[0019] M represents oxygen or sulphur,

[0020] R¹ represents in each case optionally halogen-substituted alkyl,alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionallyhalogen-, alkyl- or alkoxy-substituted cycloalkyl which may beinterrupted by at least one heteroatom, in each case optionallysubstituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl orhetaryloxyalkyl,

[0021] R² represents in each case optionally halogen-substituted alky,alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each caseoptionally substituted cycloalkyl, phenyl or benzyl,

[0022] R³ represents optionally halogen-substituted alkyl or optionallysubstituted phenyl,

[0023] R⁴ and R⁵ independently of one another each represent in eachcase optionally halogen-substituted alkyl, alkoxy, alkylamino,dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent ineach case optionally substituted phenyl, benzyl, phenoxy or phenylthioand

[0024] R⁶ and R⁷ independently of one another each represent hydrogen,in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl,alkoxy, alkoxyalkyl, represent optionally substituted phenyl, representoptionally substituted benzyl or together with the N atom to which theyare attached represent an optionally substituted ring which isoptionally interrupted by oxygen or sulphur

[0025] and at least one agonist or antagonist of acetylcholine receptorsof the formula (HI) are synergistically active and are suitable forcontrolling animal pests.

[0026] Depending inter alia on the nature of the substituents, thecompounds of the formula (I) can be present as geometrical and/oroptical isomers or isomer mixtures of varying composition, which, ifappropriate, can be separated in a customary manner. The presentinvention provides both the pure isomers and the isomer mixtures, theirpreparation and use, and compositions comprising them. Hereinbelow, forthe sake of simplicity, only compounds of the formula (I) are referredto, although this means both the pure compounds and, if appropriate,mixtures with varying proportions of isomeric compounds.

[0027] The agonists and antagonists of the nicotinic acetylcholinereceptors are known compounds which are known from the followingpublications:

[0028] European Published Specifications Nos. 464 830, 428 941, 425 978,386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725,212 600, 192 060, 163 855, 154 178, 136 636, 136 686, 303 570, 302 833,306 696, 189 972, 455 000, 135 956, 471 372, 302 389, 428 941, 376 279,493 369, 580 553, 649 845, 685 477, 483 055,580 553;

[0029] German Offenlegungsschriften Nos. 3 639 877, 3 712 307;

[0030] Japanese Published Specifications Nos. 03 220 176, 02 207 083, 63307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072, 05 178833, 07 173 157, 08 291 171;

[0031] U.S. Pat. Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686,5,034,404, 5,532,365;

[0032] PCT Applications Nos. WO 91/17 659, 91/4965;

[0033] French Application No. 2 611 114;

[0034] Brazilian Application No. 88 03 621.

[0035] The generic formulae and definitions described in thesepublications, and also the individual compounds described therein, areexpressly incorporated herein by reference.

[0036] Some of these compounds are summarized under the termnitromethylenes, nitroimines and related compounds.

[0037] Preferably, these compounds can be summarized under the formula(II)

[0038] in which

[0039] R represents hydrogen or represents optionally substitutedradicals selected from the group consisting of acyl, alkyl, aryl,aralkyl, heterocyclyl, heteroaryl and heteroarylalkyl;

[0040] A′ represents a monofunctional group selected from the groupconsisting of hydrogen, acyl, alkyl, aryl or represents a bifunctionalgroup which is linked to the radical Z′;

[0041] E′ represents an electron-withdrawing radical;

[0042] X′ represents the radicals —CH═ or ═N—, where the radical —CH═may be linked to the radical Z′ instead of an H atom;

[0043] Z′ represents a monofunctional group selected from the groupconsisting of alkyl, —O—R, —S—R,

[0044] where the radicals R are identical or different and are asdefined above,

[0045] or represents a bifunctional group which is linked to the radicalA′ or to the radical X′.

[0046] Particular preference is given to compounds of the formula (II)in which the radicals have the following meaning:

[0047] R represents hydrogen and represents optionally substitutedradicals selected from the group consisting of acyl, alkyl, aryl,aralkyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl.

[0048] Examples of acyl radicals are formyl, alkylcarbonyl,arylcarbonyl, alkylsulphonyl, arylsulphonyl,(alkyl-)-(aryl-)-phosphoryl, which may themselves be substituted.

[0049] Examples of alkyl are C₁-C₁₀-alkyl, in particular C₁-C₄-alkyl,specifically methyl, ethyl, i-propyl, sec- or t-butyl, which maythemselves be substituted.

[0050] Examples of aryl are phenyl, naphthyl, in particular phenyl.

[0051] Examples of aralkyl are phenylmethyl, phenethyl.

[0052] An example of heterocyclylalkyl is the radical

[0053] Examples of heteroaryl are heteroaryl having up to 10 ring atomsand N, O, S, in particular N, as heteroatoms. Specific examples arethienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl,pyridazinyl.

[0054] Examples of heteroarylalkyl are heteroarylmethyl, heteroarylethylhaving up to 6 ring atoms and N, O, S, in particular N, as heteroatoms,in particular optionally substituted heteroaryl as defined underheteroaryl.

[0055] Substituents which may be mentioned by way of example and by wayof preference are:

[0056] alkyl having preferably 1 to 4, in particular 1 or 2, carbonatoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl;alkoxy having preferably 1 to 4, in particular 1 or 2, carbon atoms,such as methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy;alkylthio having preferably 1 to 4, in particular 1 or 2, carbon atoms,such as methylthio, ethylthio, n- and i-propylthio and n-, i- andt-butylthio; halogenoalkyl having preferably 1 to 4, in particular 1 or2, carbon atoms and preferably 1 to 5, in particular 1 to 3, halogenatoms, the halogen atoms being identical or different, and preferredhalogen atoms being fluorine, chlorine or bromine, in particularfluorine, such as trifluoromethyl, hydroxyl; halogen, preferablyfluorine, chlorine, bromine and iodine, in particular fluorine, chlorineand bromine, cyano; nitro; amino; monoalkyl- and dialkylamino havingpreferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group,such as methylamino, methylethylamino, n- and i-propylamino andmethyl-n-butylamino; carboxyl; carbalkoxy having preferably 2 to 4, inparticular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy;sulpho (—SO₃H); alkylsulphonyl having preferably 1 to 4, in particular 1or 2, carbon atoms, such as methylsulphonyl and ethylsulphonyl;arylsulphonyl having preferably 6 or 10 aryl carbon atoms, such asphenylsulphonyl, and also heteroarylamino and heteroarylalkylamino suchas chloropyridylamino and chloropyridylmethylamino.

[0057] A′ represents hydrogen or represents an optionally substitutedradical selected from the group consisting of acyl, alkyl, aryl, whichare preferably as defined under R, A′ furthermore represents abifunctional group. Examples include optionally substituted alkylenehaving 1 to 4, in particular 1 or 2, C atoms, examples of substituentsbeing the substituents which have been listed further above (and wherethe alkylene groups may be interrupted by heteroatoms from the groupconsisting of N, O, S).

[0058] A′ and Z′ together with the atoms to which they are attached mayform a saturated or unsaturated heterocyclic ring. The heterocyclic ringmay contain a further 1 or 2 identical or different heteroatoms and/orhetero groups. Preferred heteroatoms are oxygen, sulphur or nitrogen,and preferred hetero groups are N-alkyl, where the alkyl of the N-alkylgroup contains preferably 1 to 4, in particular 1 or 2, carbon atoms.Examples of alkyl include methyl, ethyl, n- and i-propyl, and n-, i- andt-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ringmembers.

[0059] Examples of compounds of the formula (II) in which A′ and Z′together with the atoms to which they are attached form a ring includethe following:

[0060] in which

[0061] E′, R and X′ are each as defined above and further below.

[0062] E′ represents an electron-withdrawing radical, specific examplesbeing NO₂, CN, halogenoalkylcarbonyl, such ashalogeno-C₁-C₄-alkylcarbonyl, for example COCF₃, alkylsulphonyl (forexample SO₂—CH₃), halogenoalkylsulphonyl (for example SO₂CF₃) and withparticular preference NO₂ or CN.

[0063] X′ represents —CH═ or —N═.

[0064] Z′ represents an optionally substituted radical selected from thegroup consisting of alkyl, —OR, —SR, —NRR, where R and the substituentsare preferably as defined above.

[0065] Z′ may, in addition to the ring mentioned above, together withthe atom to which it is attached and the radical

[0066] instead of X′, form a saturated or unsaturated heterocyclic ring.The heterocyclic ring may contain a further 1 or 2 identical ordifferent heteroatoms and/or hetero groups. Preferred heteroatoms areoxygen, sulphur or nitrogen and preferred hetero groups are N-alkyl,where the alkyl or N-alkyl group contains preferably 1 to 4, preferably1 or 2, carbon atoms. Examples of alkyl include methyl, ethyl, n- andi-propyl and n-, i- and t-butyl. The heterocyclic ring contains 5 to 7,preferably 5 or 6, ring members. Examples of the heterocyclic ringinclude pyrrolidine, piperidine, piperazine, hexamethylenimine,morpholine and N-methylpiperazine.

[0067] The agonists and antagonists of the nicotinic acetylcholinereceptors are particularly preferably compounds of the formula (II) inwhich

[0068] R represents

[0069] where

[0070] n represents 0, 1 or 2, and preferably represents 1,

[0071] Subst. represents one of the substituents mentioned above,especially halogen, in particular chlorine, and A′, Z′, X′ and E′ areeach as defined above.

[0072] R represents in particular

[0073] The following compounds are specific examples:

[0074] Very particularly preferred agonists and antagonists of thenicotinic acetylcholine receptors are compounds of the followingformulae:

[0075] in particular a compound of the following formula

[0076] Very particular preference is given to the compounds of theformulae (IIa) and (IIk).

[0077] Furthermore, very particular preference is given to the compoundsof the formulae (IIe), (IIg), (IIh), (III), (IIc) and (IIm).

[0078] Preference is given to active compound combinations comprisingcompounds of the formula (I) in which the radicals are as defined below:

[0079] W preferably represents hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,chlorine, bromine or fluorine,

[0080] X preferably represents C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-halogenoalkyl, fluorine, chlorine or bromine,

[0081] Y and Z independently of one another each preferably representhydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy or C₁-C₄-halogenoalkyl,

[0082] A preferably represents hydrogen or in each case optionallyhalogen-substituted C₁-C₆-alkyl or C₃-C₈-cycloalkyl,

[0083] B preferably represents hydrogen, methyl or ethyl,

[0084] A, B and the carbon atom to which they are attached preferablyrepresent saturated C₃-C₆-cycloalkyl in which optionally one ring memberis replaced by oxygen or sulphur and which is optionally mono- ordisubstituted by C₁-C₄-alkyl, trifluoromethyl or C₁-C₄-alkoxy,

[0085] D preferably represents hydrogen, in each case optionallyfluorine- or chlorine-substituted C₁-C₆-alkyl, C₃-C₄-alkenyl orC₃-C₆-cycloalkyl,

[0086] A and D together preferably represent in each case optionallymethyl-substituted C₃-C₄-alkanediyl in which optionally one methylenegroup is replaced by sulphur.

[0087] G preferably represents hydrogen (a) or represents one of thegroups

[0088] E^((f)) and

[0089] in particular (a), (b), (c) or (g) in which

[0090] E represents a metal ion or an ammonium ion,

[0091] L represents oxygen or sulphur and

[0092] M represents oxygen or sulphur,

[0093] R¹ preferably represents in each case optionallyhalogen-substituted C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C4-alkylthio-C₁-C₄-alkyl or optionallyfluorine-, chlorine-, C₁-C₄-alkyl- or C₁-C₂-alkoxy-substitutedC₃-C₆-cycloalkyl,

[0094] represents optionally fluorine-, chlorine-, bromine-, cyano-,nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl- ortrifluoromethoxy-substituted phenyl,

[0095] represents in each case optionally chlorine- ormethyl-substituted pyridyl or thienyl,

[0096] R² preferably represents in each case optionally fluorine- orchlorine-substituted C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl,C₁-C₄-alkoxy-C₂-C₄-alkyl,

[0097] represents optionally methyl- or methoxy-substitutedC₅-C₆-cycloalkyl or

[0098] represents in each case optionally fluorine-, chlorine-,bromine-, cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl-or trifluoromethoxy-substituted phenyl or benzyl,

[0099] R³ preferably represents optionally fluorine-substitutedC₁-C₄-alkyl or represents optionally fluorine-, chlorine-, bromine-,C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl-, trifluoromethoxy-, cyano-or nitro-substituted phenyl,

[0100] R⁴ preferably represents in each case optionally fluorine- orchlorine-substituted C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,C₁-C₄-alkylthio or represents in each case optionally fluorine-,chlorine-, bromine-, nitro-, cyano-, C₁-C₄-alkoxy-, trifluoromethoxy-,C₁-C₄-alkylthio-, C₁-C₄-halogenoalkylthio-, C₁-C₄-alkyl- ortrifluoromethyl-substituted phenyl, phenoxy or phenylthio,

[0101] R⁵ preferably represents C₁-C₄-alkoxy or C₁-C₄-thioalkyl,

[0102] R⁶ preferably represents C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₁-C₆-alkoxy, C₃-C₆-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,

[0103] R⁷ preferably represents C₁-C₆-alkyl, C₃-C₆-alkenyl orC₁-C₄-alkoxy-C₁-C₄-alkyl,

[0104] R⁶ and R⁷ together preferably represent an optionally methyl- orethyl-substituted C₃-C₆-alkylene radical in which optionally one carbonatom is replaced by oxygen or sulphur,

[0105] W particularly preferably represents hydrogen, methyl, ethyl,chlorine, bromine or methoxy,

[0106] X particularly preferably represents chlorine, bromine, methyl,ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,

[0107] Y and Z independently of one another each represent hydrogen,fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl,trifluoromethyl or methoxy,

[0108] A particularly preferably represents methyl, ethyl, propyl,i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, cyclopropyl,cyclopentyl or cyclohexyl,

[0109] B particularly preferably represents hydrogen, methyl or ethyl,

[0110] A, B and the carbon atom to which they are attached particularlypreferably represent saturated C₆-Cycloalkyl in which optionally onering member is replaced by oxygen and which is optionallymonosubstituted by methyl, ethyl, methoxy, ethoxy, propoxy or butoxy,

[0111] D particularly preferably represents hydrogen, represents methyl,ethyl, propyl, i-propyl, butyl, i-butyl, allyl, cyclopropyl, cyclopentylor cyclohexyl,

[0112] A and D together particularly preferably represent optionallymethyl-substituted C₃-C₄-alkanediyl,

[0113] G particularly preferably represents hydrogen (a) or representsone of the groups

[0114] in which

[0115] M represents oxygen or sulphur,

[0116] R¹ particularly preferably represents C₁-C₈-alkyl, C₂-C₄-alkenyl,methoxymethyl, ethoxymethyl, ethylthiomethyl, cyclopropyl, cyclopentylor cyclohexyl,

[0117] represents optionally fluorine-, chlorine-, bromine-, cyano-,nitro-, methyl-, ethyl-, methoxy-, trifluoromethyl- ortrifluoromethoxy-substituted phenyl,

[0118] represents in each case optionally chlorine- ormethyl-substituted pyridyl or thienyl,

[0119] R² particularly preferably represents C₁-C₈-alkyl, C₂-C₄-alkenyl,methoxyethyl, ethoxyethyl or represents phenyl or benzyl,

[0120] R⁶ and R⁷ independently of one another each particularlypreferably represent methyl or ethyl or together represent a C₅-alkyleneradical in which the C₃-methylene group is replaced by oxygen.

[0121] W very particularly preferably represents hydrogen or methyl,

[0122] X very particularly preferably represents chlorine, bromine ormethyl,

[0123] Y and Z independently of one another each very particularlypreferably represent hydrogen, chlorine, bromine or methyl,

[0124] A, B and the carbon atom to which they are attached veryparticularly preferably represent saturated C₆-cycloalkyl in whichoptionally one ring member is replaced by oxygen and which is optionallymonosubstituted by methyl, methoxy, ethoxy, propoxy or butoxy,

[0125] D very particularly preferably represents hydrogen,

[0126] G very particularly preferably represents hydrogen (a) orrepresents one of the groups

[0127] in which

[0128] M represents oxygen or sulphur,

[0129] R¹ very particularly preferably represents C₁-C₈-alkyl,C₂-C₄-alkenyl, methoxymethyl, ethoxymethyl, ethylmethylthio,cyclopropyl, cyclopentyl, cyclohexyl or

[0130] represents optionally fluorine-, chlorine-, bromine-, methyl-,methoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- ornitro-substituted phenyl,

[0131] represents in each case optionally chlorine- ormethyl-substituted pyridyl or thienyl,

[0132] R² very particularly preferably represents C₁-C₈-alkyl,C₂-C₄-alkenyl, methoxyethyl, ethoxyethyl, phenyl or benzyl,

[0133] R⁶ and R⁷ independently of one another each very particularlypreferably represent methyl, ethyl or together represent a C₅-alkyleneradical in which the C₃-methylene group is replaced by oxygen.

[0134] Particular preference is given to active compound combinationscomprising the following compounds of the formula (I) (I)

Example No. W X Y Z R G m.p. ° C. I-1 H Br 5-CH₃ H OCH₃ CO—i-C₃H₇ 122I-2 H Br 5-CH₃ H OCH₃ CO₂—C₂H₅ 140-142 I-3 H CH₃ 5-CH₃ H OCH₃ H >220  I-4 H CH₃ 5-CH₃ H OCH₃ CO₂—C₂H₅ 128 I-5 CH₃ CH₃ 3-Br H OCH₃ H >220   I-6CH₃ CH₃ 3-Cl H OCH₃ H 219 I-7 H Br 4-CH₃ 5-CH₃ OCH₃ CO—i-C₃H₇ 217 I-8 HCH₃ 4-Cl 5-CH₃ OCH₃ CO₂C₂H₅ 162 I-9 H CH₃ 4-CH₃ 5-CH₃ OCH₃

Oil I-10 CH₃ CH₃ 3-CH₃ 4-CH₃ OCH₃ H >220   I-11 H CH₃ 5-CH₃ H OC₂H₅

Oil I-12 CH₃ CH₃ 3-Br H OC₂H₅ CO—i-C₃H₇ 212-214 I-13 H CH₃ 4-CH₃ 5-CH₃OC₂H₅ CO—n-Pr 134 I-14 H CH₃ 4-CH₃ 5-CH₃ OC₂H₅ CO—i-Pr 108 I-15 H CH₃4-CH₃ 5-CH₃ OC₂H₅ CO—c-Pr 163

[0135] The active compound combinations being well tolerated by plantsand non-toxic to warm-blooded animals are suitable for controllinganimal pests, in particular insects, arachnids and nematodes found inagriculture, in forests, in the protection of stored products andmaterials and in the hygiene sector. They are preferably used as cropprotection agents. They are active against normally sensitive andresistant species, and against all or individual developmental stages.The abovementioned pests include:

[0136] From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare, Porcellio scaber.

[0137] From the order of the Diplopoda, for example, Blaniulusguttulatus.

[0138] From the order of the Chilopoda, for example, Geophiluscarpophagus, Scutigera spp.

[0139] From the order of the Symphyla, for example, Scutigerellaimmaculata.

[0140] From the order of the Thysanura, for example, Lepisma saccharina.

[0141] From the order of the Collembola, for example, Onychiurusarmatus.

[0142] From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.,Schistocerca gregaria.

[0143] From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica.

[0144] From the order of the Dermaptera, for example, Forficulaauricularia.

[0145] From the order of the Isoptera, for example. Reticulitermes spp.

[0146] From the order of the Phthiraptera, for example, Pediculushumanus corporis, Haematopinus spp., Linognathus spp., Trichodectesspp., Damalinia spp.

[0147] From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

[0148] From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Tnratoma spp.

[0149] From the order of the Homoptera, for example, Aleurodesbrassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi,Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix,Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli,Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettixcincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus,Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,Pseudococcus spp., Psylla spp.

[0150] From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pornonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp., Oulema oryzae.

[0151] From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon soistitialis, Costelytra zealandica, Lissorhoptrusoryzophilus.

[0152] From the order of the Hymenoptera, for example, Diprion spp.,Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

[0153] From the order of the Diptera, for example, Aedes spp., Anophelesspp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebraspp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp., Liriomyza spp.

[0154] From the order of the Siphonaptera, for example, Xenopsyllacheopis, Ceratophyllus spp.

[0155] From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp.,Dernanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp., Brevipalpus spp.

[0156] The plant-parasitic nematodes include, for example, Pratylenchusspp., Radopholus similis, Ditylenchus dipsaci, Tylenchulussemipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp.,Aphelenchoides spp., Longidorus spp., xiphinema spp., Trichodorus spp.,Bursaphelenchus spp.

[0157] According to the invention, it is possible to treat all plantsand parts of plants. Plants are to be understood here as meaning allplants and plant populations such as desired and undesired wild plantsor crop plants (including naturally occurring crop plants). Crop plantscan be plants which can be obtained by conventional breeding andoptimization methods or by biotechnological and genetic engineeringmethods or combinations of these methods, including the transgenicplants and including the plant cultivars which can or cannot beprotected by plant breeders' certificates. Parts of plants are to beunderstood as meaning all above-ground and below-ground parts and organsof plants, such as shoot, leaf, flower and root, examples which may bementioned being leaves, needles, stems, trunks, flowers, fruit-bodies,fruits and seeds and also roots, tubers and rhizomes. Parts of plantsalso include harvested plants and vegetative and generative propagationmaterial, for example seedlings, tubers, rhizomes, cuttings and seeds.

[0158] The treatment according to the invention of the plants and partsof plants with the compounds of the formula (I) alone and in particularwith the active compound combinations is carried out directly or byaction on their environment, habitat or storage area according tocustomary treatment methods, for example by dipping, spraying,evaporating, atomizing, broadcasting, brushing-on and, in the case ofpropagation material, in particular in the case of seeds, furthermore byone- or multi-layer coating.

[0159] As already mentioned above, it is possible to treat all plantsand their parts according tQ the invention. In a preferred embodiment,wild plant species and plant cultivars, or those obtained byconventional biological breeding methods, such as crossing or protoplastfusion, and parts thereof, are treated. In a further preferredembodiment, transgenic plants and plant cultivars obtained by geneticengineering, if appropriate in combination with conventional rmethods(Genetically Modified Organisms), and parts thereof are treated. Theterm “parts” or “parts of plants” or “plant parts” has been explainedabove.

[0160] Particularly preferably, plants of the plant cultivars which arein each case commercially available or in use are treated according tothe invention.

[0161] Depending on the plant species or plant cultivars, their locationand growth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, better quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possiblewhich exceed the effects which were actually to be expected.

[0162] The transgenic plants or plant cultivars (i.e. those obtained bygenetic engineering) which are preferred and to be treated according tothe invention include all plants which, in the genetic modification,received genetic material which imparts particularly advantageous usefultraits to these plants. Examples of such properties are better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, better quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch properties are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape andalso fruit plants (with the fruits apples, pears, citrus fruits andgrapes), and particular emphasis is given to maize, soya beans,potatoes, cotton and oilseed rape. Traits that are particularlyemphasized are the increased defence of the plants against insects bytoxins formed in the plants, in particular those formed by the geneticmaterial from Bacillus thuringiensis (for example by the genes CryIA(a),CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb andCryIF and also combinations thereof) (hereinbelow referred to as “Btplants”). Traits that are furthermore particularly emphasized are theincreased tolerance of the plants to certain herbicidally activecompounds, for example imidazolinones, sulphonylureas, glyphosate orphosphinotricin (for example the “PAT” gene). The genes which impart thedesired traits in question can also be present in combination with oneanother in the transgenic plants. Examples of “Bt plants” which may bementioned are maize varieties, cotton varieties, soya bean varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya beans), KnockOut® (for example maize),StarLink(® (for example maize), Bollgard® (cotton), Nucotn® (cotton) andNewLeaf® (potato). Examples of herbicide-tolerant plants which may bementioned are maize varieties, cotton varieties and soya bean varietieswhich are sold under the trade names Roundup Ready® (tolerance toglyphosate, for example maize, cotton, soya bean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize). Of course, these statements also apply to plant cultivars havingthese or still-to-be-developed genetic traits, which plants will bedeveloped and/or marketed in the future.

[0163] The plants listed can be treated according to the invention in aparticularly advantageous manner with the active compound mixturesaccording to the invention. The preferred ranges stated above for themixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the mixturesspecifically mentioned in the present text.

[0164] The ratio of the compounds of the formula (I) and the compoundsof the formula (II) used, and the total amount of the mixture, dependson the nature and the occurrence of the insects. For each application,optimum ratios and total amounts used can in each case be determined bytest series. In general, the ratio of compounds of the formula (I) tocompounds of the formula (II) is from 1:100 to 100:1, preferably from1:25 to 25:1 and particularly preferably from 1:5 to 5:1. These areparts by weight.

[0165] The active compound combinations can be converted into thecustomary formulations such as solutions, emulsions, wettable powders,suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and microencapsulations in polymericmaterials.

[0166] These formulations are produced in a known manner, for example bymixing the active compounds with extenders, that is liquid solventsand/or solid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam formers.

[0167] If the extender used is water, it is also possible, for example,to use organic solvents as cosolvents. The following are essentiallysuitable as liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

[0168] Suitable solid carriers are:

[0169] for example ammonium salts and ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic materials such ashighly-disperse silica, alumina and silicates; suitable solid carriersfor granules are: for example crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, or elsesynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks; suitable emulsifiers and/or foam formers are: for examplenonionic and anionic emulsifiers such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates; suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

[0170] Tackifiers such as carboxymethylcellulose and natural andsynthetic polymers in the form of powders, granules or latices, such asgum arabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

[0171] It is possible to use colorants such as inorganic pigments, forexample iron oxide, titanium oxide and Prussian Blue, and organiccolorants such as alizarin colorants, azo colorants and metalphthalocyanine colorants, and trace nutrients such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc.

[0172] The formulations generally comprise between 0.1 and 95% by weightof active compound, preferably between 0.5 and 90%.

[0173] The active compound combinations according to the invention canbe present in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with other activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth-regulating substances orherbicides. The insecticides include, for example, phosphates,carbamates, carboxylates, chlorinated hydrocarbons, phenylureas andsubstances produced by microorganisms, inter alia.

[0174] Examples of suitable mixing components are the following:

[0175] Fungicides:

[0176] aldimorph, ampropylfos, ampropylfos potassium, andoprim,anilazine, azaconazole, azoxystrobin,

[0177] benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

[0178] calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

[0179] debacarb, dichlorophen, diclobutrazole, diclofluanid,diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol,dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine,dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

[0180] edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

[0181] famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodi um, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox,

[0182] guazatine,

[0183] hexachlorobenzene, hexaconazole, hymexazole,

[0184] imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

[0185] kasugamycin, kresoxim-methyl, copper preparations, such as:copper hydroxide, copper naphthenate, copper oxychloride, coppersulphate, copper oxide, oxine-copper and Bordeaux mixture,

[0186] mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

[0187] nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

[0188] ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,oxyfenthiin,

[0189] paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

[0190] quinconazole, quintozene (PCNB),

[0191] sulphur and sulphur preparations,

[0192] tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazole,

[0193] uniconazole,

[0194] validamycin A, vinclozolin, viniconazole,

[0195] zarilamide, zineb, ziram and also

[0196] Dagger G,

[0197] OK-8705,

[0198] OK-8801,

[0199]α-(1,1-dimethylethyl)-β(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

[0200]α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,

[0201]α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,

[0202]α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

[0203](5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

[0204] (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

[0205] 1-isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,

[0206] 1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanoneO-(phenylmethyl)-oxime,

[0207] 1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

[0208] 1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

[0209] 1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

[0210]1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

[0211]1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

[0212]1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

[0213] 1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,

[0214]2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

[0215]2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

[0216] 2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,

[0217] 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

[0218] 2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

[0219] 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

[0220]2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

[0221]2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

[0222] 2-aminobutane,

[0223] 2-bromo-2-(bromomethyl)-pentanedinitrile,

[0224]2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

[0225]2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

[0226] 2-phenylphenol (OPP),

[0227] 3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,

[0228]3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

[0229] 3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

[0230] 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

[0231]4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

[0232] 4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

[0233]8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

[0234] 8-hydroxyquinoline sulphate,

[0235] 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,

[0236]bis-(1-methylethyl)-3-methyl-[(3-methylbenzoyl)-oxyl-2,5-thiophenedicarboxylate

[0237] cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

[0238]cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,

[0239] ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

[0240] potassium hydrogen carbonate,

[0241] methanetetrathiol sodium salt,

[0242] methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

[0243] methylN-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

[0244] methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

[0245] N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,

[0246]N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

[0247]N-(9,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

[0248] N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

[0249] N-(4cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

[0250] N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

[0251]N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

[0252] N-(6-methoxy-3-pyridinyl)-yclopropanecarboxamide,

[0253] N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,

[0254]N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,

[0255] N-formyl-N-hydroxy-DL-alanine-sodium salt,

[0256] O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

[0257] O-methyl S-phenyl phenylpropylphosphoramidothioate,

[0258] S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

[0259] spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,

[0260] Bactericides:

[0261] bronopol, dichlorophen, nitrapyrin, nickeldimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid,oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphateand other copper preparations.

[0262] Insecticides/Acaricides/Nematicides:

[0263] abamectin, acephate, acetamiprid, acrinathrin, alanycarb,aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz,avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphosM, azocyclotin,

[0264]Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis,Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveriatenella, bendiocarb, benfuracarb, bensultap, benzoximate,betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin,BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,butylpyridaben,

[0265] cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb,clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin,cyhalothrin, cyhexatin, cypermethrin, cyromazine,

[0266] deltamethrin, demeton M, demeton S, demeton-S-methyl,diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat,dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,

[0267] eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthoraspp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox,etoxazole, etrimfos,

[0268] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam,fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox,furathiocarb,

[0269] granulosis viruses,

[0270] halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,hydroprene,

[0271] imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

[0272] nuclear polyhedrosis viruses,

[0273] lambda-cyhalothrin, lufenuron,

[0274] malathion, mecarbam, metaldehyde, methamidophos, Metharhiziumanisopliae, Metharhizium flavoviride, methidathion, methiocarb,methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, monocrotophos,

[0275] naled, nitenpyram, nithiazine, novaluron,

[0276] omethoat, oxamyl, oxydemethon M,

[0277]Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb,pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos,prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben,pyridathion, pyrimidifen, pyriproxyfen,

[0278] quinalphos,

[0279] ribavirin,

[0280] salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,

[0281] tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,trimethacarb,

[0282] vamidothion, vaniliprole, Verticillium lecanii

[0283] YI 5302

[0284] zeta-cyperrnethrin, zolaprofos

[0285](1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,

[0286] (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanec arboxylate,

[0287]1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,

[0288]2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]4,5-dihydro-oxazole,

[0289] 2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,

[0290]2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,

[0291]2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,

[0292] 3-methylphenyl propylcarbamate

[0293] 4-[4-(4-ethoxyphenyl)-4-methylpentyl)-1-fluoro-2-phenoxy-benzene,

[0294]4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,

[0295]4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,

[0296]4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,

[0297] Bacillus thuringiensis strain EG-2348,

[0298] [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,

[0299]2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-ylbutanoate,

[0300][3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,

[0301] dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde

[0302] ethyl[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxylethyl]-carbamate

[0303] N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine

[0304]N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,

[0305] N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,

[0306] N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,

[0307] N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,

[0308] O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

[0309] Mixtures with other known active compounds such as herbicides orwith fertilizers and growth regulators are also possible.

[0310] When used as insecticides, the active compound combinationsaccording to the invention can furthermore be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with synergists. Synergists arecompounds which increase the action of the active compounds, without itbeing necessary for the synergist added to be active itself.

[0311] The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

[0312] The compounds are employed in a customary manner appropriate forthe use forms.

[0313] When used against hygiene pests and stored-product pests, theactive compound combinations are distinguished by an excellent residualaction on wood and clay as well as good stability to alkali on limedsubstrates.

[0314] The active compound combinations according to the invention arenot only active against plant pests, hygiene pests and stored-productpests, but also, in the veterinary medicine sector, against animalparasites (ectoparasites) such as hard ticks, soft ticks, mange mites,harvest mites, flies (stinging and licking), parasitizing fly larvae,lice, hair lice, bird lice and fleas. These parasites include:

[0315] From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

[0316] From the order of the Mallophagida and the suborders Amblycerinaand Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinotonspp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

[0317] From the order Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

[0318] From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

[0319] From the order of the Heteropterida, for example, Cimex spp.,Triatoma spp., Rhodnius spp., Panstrongylus spp.

[0320] From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

[0321] From the subclass of the Acaria (Acarida) and the orders of theMeta- and Mesostigmata, for example, Argas spp., Omithodorus spp.,Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentorspp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dernanyssusspp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

[0322] From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

[0323] The active compound combinations according to the invention arealso suitable for controlling arthropods which attack agriculturallivestock such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese,honey-bees, other domestic animals such as, for example, dogs, cats,caged birds, aquarium fish and so-called experimental animals such as,for example, hamsters, guinea pigs, rats and rnice. By controlling thesearthropods, cases of death and reductions in productivity (for meat,milk, wool, hides, eggs, honey and the like) should be diminished, sothat more economical and simpler animal husbandry is possible by the useof the active compound combinations according to the invention.

[0324] The active compound combinations according to the invention areused in the veterinary sector in a known manner by enteraladministration in the form of, for example, tablets, capsules, potions,drenches, granules, pastes, boluses, the feed-through method,suppositories, by parenteral administration such as, for example, byinjections (intramuscularly, subcutaneously, intravenously,intraperitoneally and the like), implants, by nasal administration, bydermal administration in the form of, for example, immersing or dipping,spraying, pouring-on, spotting-on, washing, dusting, and with the aid ofactive-compound-comprising moulded articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

[0325] When used for cattle, poultry, domestic animals and the like, theactive compounds can be applied as formulations (for example powders,emulsions, flowables) comprising the active compounds in an amount of 1to 80% by weight, either directly or after 100- to 10,000-fold dilution,or they may be used as a chemical dip.

[0326] Moreover, it has been found that the active compound combinationsaccording to the invention show a potent insecticidal action againstinsects which destroy industrial materials.

[0327] The following insects may be mentioned by way of example and withpreference, but not by way of limitation:

[0328] Beetles such as

[0329]Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylonaequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apatemonachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylonspec., Dinoderus minutus.

[0330] Dermapterans such as

[0331]Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerusaugur.

[0332] Termnites such as

[0333]Kalotermes flavicollis, Cryptotermes brevis, Heterotermesindicola, Reticulitermes flavipes, Reticulitermes santonensis,Reticulitermes lucifugus, Mastotermes darwiniensis, Zooternopsisnevadensis, Coptotermes formosanus.

[0334] Bristle-tails such as Lepisma saccharina.

[0335] Industrial materials in the present context are understood asmeaning non-living materials such as, preferably, polymers, adhesives,glues, paper and board, leather, wood, timber products and paints.

[0336] The material which is to be protected from insect attack is veryparticularly preferably wood and timber products.

[0337] Wood and timber products which can be protected by thecomposition according to the invention, or mixtures comprising it, areto be understood as meaning, for example:

[0338] Construction timber, wooden beams, railway sleepers, bridgecomponents, jetties, vehicles made of wood, boxes, pallets, containers,telephone poles, wood lagging, windows and doors made of wood, plywood,chipboard, joinery, or timber products which quite generally are used inhouse construction or building joinery.

[0339] The active compound combinations can be used as such, in the formof concentrates or generally customary formulations such as powders,granules, solutions, suspensions, emulsions or pastes.

[0340] The abovementioned formulations can be prepared in a manner knownper se, for example by mixing the active compounds with at least onesolvent or diluent, emulsifier, dispersant and/or binder or fixative,water repellant, if desired desiccants and UV stabilizers, and ifdesired colorants and pigments and other processing auxiliaries.

[0341] The insecticidal compositions or concentrates used for protectingwood and timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

[0342] The amount of composition or concentrate employed depends on thespecies and the abundance of the insects and on the medium. The optimalquantity to be employed can be determined in each case by test seriesupon application. In general, however, it will suffice to employ 0.0001to 20% by weight, preferably 0.001 to 10% by weight, of the activecompound, based on the material to be protected.

[0343] A suitable solvent and/or diluent is an organochemical solvent orsolvent mixture and/or an oily or oil-type organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetter.

[0344] Organochemical solvents which are preferably employed are oily oroil-type solvents with an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. Such oily and oil-typesolvents which are insoluble in water and of low volatility and whichare used are suitable mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

[0345] Mineral oils with a boiling range of 170 to 220° C., white spiritwith a boiling range of 170 to 220° C., spindle oil with a boiling rangeof 250 to 350° C., petroleum and aromatics with a boiling range of 160to 280° C., oil of terpentine, and the like are advantageously used.

[0346] In a preferred embodiment, liquid aliphatic hydrocarbons with aboiling range of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene are used.

[0347] The organic oily or oil-type solvents of low volatility and withan evaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that theinsecticide-fungicide mixture is soluble or emulsifiable in this solventmixture.

[0348] In a preferred embodiment, some of the organochemical solvent orsolvent mixture is replaced by an aliphatic polar organochemical solventor solvent mixture. Aliphatic organochemical solvents which containhydroxyl and/or ester and/or ether groups are preferably used, such as,for example, glycol ethers, esters or the like.

[0349] Organochemical binders used for the purposes of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se and which can be diluted in water and/or dissolved ordispersed or emulsified in the organochemical solvents employed, inparticular binders composed of, or comprising, an acrylate resin, avinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenol resin, hydrocarbon resin such asindene/coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

[0350] The synthetic resin employed as binder can be employed in theform of an emulsion, dispersion or solution. Bitumen or bituminoussubstances may also be used as binders, in amounts of up to 10% byweight. In addition, colorants, pigments, water repellants,odour-masking agents, and inhibitors or anticorrosive agents and thelike, all of which are known per se, can be employed.

[0351] In accordance with the invention, the composition or theconcentrate preferably comprises, as organochemical binders, at leastone alkyd resin or modified alkyd resin and/or a drying vegetable oil.Alkyd resins which are preferably used in accordance with the inventionare those with an oil content of over 45% by weight, preferably 50 to68% by weight.

[0352] Some or all of the abovementioned binder can be replaced by afixative (mixture) or plasticizer (mixture). These additives areintended to prevent volatilization of the active compounds, and alsocrystallization or precipitation. They preferably replace 0.01 to 30% ofthe binder (based on 100l% of binder employed).

[0353] The plasticizers are from the chemical classes of the phthalicesters, such as dibutyl phthalate, dioctyl phthalate or benzyl butylphthalate, phosphoric esters such as tributyl phosphate, adipic esterssuch as di-(2-ethylhexyl)-adipate, stearates such as butyl stearate oramyl stearate, oleates such as butyl oleate, glycerol ethers orhigher-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

[0354] Fixatives are based chemically on polyvinyl alkyl ethers such as,for example, polyvinyl methyl ether, or ketones such as benzophenone andethylenebenzophenone.

[0355] Other suitable solvents or diluents are, in particular, water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

[0356] Particularly effective timber protection is achieved byindustrial-scale impregnating processes, for example the vacuum,double-vacuum or pressure processes.

[0357] The ready-to-use compositions may if appropriate also containother insecticides and if appropriate one or more additional fungicides.

[0358] The active compound combinations according to the invention canat the same time be employed for protecting objects which come intocontact with saltwater or brackish water, such as hulls, screens, nets,buildings, moorings and signalling systems, against fouling.

[0359] Fouling by sessile Oligochaeta, such as Serpulidae, and by shellsand species from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

[0360] Apart from fouling by algae, for example Ectocarpus sp. andCeramium sp., fouling by sessile Entomostraka groups, which come underthe generic term Cirripedia (cirriped crustaceans), is of particularimportance.

[0361] Surprisingly, it has now been found that the active compoundcombinations according to the invention have an outstanding antifoulingaction.

[0362] Using the active compound combinations according to theinvention, allows the use of heavy metals such as, for example, inbis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltinchloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds substantially reduced.

[0363] If appropriate, the ready-to-use antifouling paints canadditionally comprise other active compounds, preferably algicides,fungicides, herbicides, molluscicides, or other antifouling activecompounds.

[0364] Preferably suitable components in combinations with theantifouling compositions according to the invention are:

[0365] algicides such as

[0366] 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,dichlorophen, diuron, endothal, fentin acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

[0367] fungicides such as

[0368] benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,tolylfluanid and azoles such as azaconazole, cyproconazole,epoxyconazole, hexaconazole, metconazole, propiconazole andtebuconazole;

[0369] molluscicides such as

[0370] fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarband trimethacarb; or conventional antifouling active compounds such as

[0371] 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium,copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and2,4,6-trichlorophenylmaleiimide.

[0372] The antifouling compositions used comprise the active compound ina concentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

[0373] Moreover, the antifouling compositions comprise the customarycomponents such as, for example, those described in Ungerer, Chem. Ind.1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, ParkRidge, 1973.

[0374] Besides the algicidal, fungicidal, molluscicidal active compoundsand insecticidal active compounds, antifouling paints comprise, inparticular, binders.

[0375] Examples of recognized binders are polyvinyl chloride in asolvent system, chlorinated rubber in a solvent system, acrylic resinsin a solvent system, in particular in an aqueous system, vinylchloride/vinyl acetate copolymer systems in the form of aqueousdispersions or in the form of organic solvent systems,butadiene/styrene/acrylonitrile rubbers, drying oils such as linseedoil, resin esters or modified hardened resins in combination with tar orbitumens, asphalt and epoxy compounds, small amounts of chlorine rubber,chlorinated polypropylene and vinyl resins.

[0376] If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The active compound combinationsaccording to the invention may also be incorporated into self-polishingantifouling systems.

[0377] The active compound combinations according to the invention arealso suitable for controlling animal pests, in particular insects,arachnids and mites, which are found in enclosed spaces such as, forexample, dwellings, factory halls, offices, vehicle cabins and the like.They can be employed alone or in combination with other active compoundsand auxiliaries in domestic insecticide products for controlling thesepests. They are active against sensitive and resistant species andagainst all developmental stages. These pests include:

[0378] From the order of the Scorpionidea, for example, Buthusoccitanus.

[0379] From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

[0380] From the order of the Araneae, for example, Aviculariidae,Araneidae.

[0381] From the order of the Opiliones, for example, Pseudoscorpioneschelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

[0382] From the order of the Isopoda, for example, Oniscus asellus,Porcellio scader.

[0383] From the order of the Diplopoda, for example, Blaniulusguttulatus, Polydesmus spp.

[0384] From the order of the Chilopoda, for example, Geophilus spp.

[0385] From the order of the Zygentoma, for example, Ctenolepisma spp.,Lepisma saccharina, Lepismodes inquilinus.

[0386] From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

[0387] From the order of the Saltatoria, for example, Acheta domesticus.

[0388] From the order of the Dermaptera, for example, Forficulaauricularia.

[0389] From the order of the Isoptera, for example, Kalotermes spp.,Reticuliterrmes spp.

[0390] From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

[0391] From the order of the Coleptera, for example, Anthrenus spp.,Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinusspp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

[0392] From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipieins, Culex tarsalis, Drosophila spp., Fannia

[0393] From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonelia, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

[0394] From the order of the Siphonaptera, for example, Ctenocephalidescanis, Ctenocephalides felis, Pulex irritans, Tunga penetrans,Xenopsylla cheopis.

[0395] From the order of the Hymenoptera, for example, Camponotusherculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

[0396] From the order of the Anoplura, for example, Pediculus humanuscapitis, Pediculus humanus corporis, Phthirus pubis.

[0397] From the order of the Heteroptera, for example, Cimex hemipterus,Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

[0398] In the sector of household insecticides, the active compounds canalso be used in combination with other suitable active compounds such asphosphoric esters, carbamates, pyrethroids, growth regulators or activecompounds from other known classes of insecticides.

[0399] They are used as aerosols, pressure-free spray products, forexample pump and atomizer sprays, automatic fogging systems, foggers,foams, gels, evaporator products with evaporator tablets made ofcellulose or polymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

[0400] When using the active compound combinations according to theinvention, the application rates can be varied within a relatively widerange, depending on the type of application. In the treatment of partsof plants, the application rates of active compounds are generallybetween 0.1 and 10 000 g/ha, preferably between 10 and 1 000 giha.

[0401] The good insecticidal and acaricidal action of the activecompound combinations according to the invention can be seen from theexamples which follow. While the individual active compounds showweaknesses in their action, the combinations show an action whichexceeds a simple sum of actions.

[0402] A synergistic effect in insecticides and acaricides is alwayspresent when the action of the active compound combinations exceeds thetotal of the actions of the active compounds when applied individually.

[0403] The expected action for a given combination of two activecompounds can be calculated as follows, using the formula of S. R.Colby, Weeds 15 (1967), 20-22:

[0404] If

[0405] X is the kill rate when employing active compound A at anapplication rate of m g/ha or in a concentration of m ppm,

[0406] Y is the kill rate when employing active compound B at anapplication rate of n g/ha or in a concentration of n ppm and

[0407] E is the kill rate when employing active compounds A and B atapplication rates of m and n g/ha or in a concentration of m and n ppm,

[0408] then $E = {X + Y - \frac{X \cdot Y}{100}}$

[0409] Here, the kill rate is determined in %. 0% means a kill ratewhich corresponds to that of the control, whereas a kill rate of 100%means that no infestation is observed.

[0410] If the actual effect exceeds the calculated value, the action ofthe combination is superadditive, i.e. a synergistic effect is present.In this case, the actually observed kill rate must exceed the valuecalculated using the above formula for the expected kill rate (E).

EXAMPLE A

[0411] Aphis Gossypii Test

[0412] Solvent: 3 parts by weight of dimethylformamide

[0413] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0414] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted with water to the desiredconcentrations.

[0415] Cotton leaves (Gossypium hirsutum) which are heavily infested bythe cotton aphid (Aphis gossypii) are treated by being dipped into thepreparation of active compound of the desired concentration.

[0416] After the desired period of time, the kill in % is determined.100% means that all aphids have been killed; 0% means that none of theaphids have been killed. The kill rates that are determined arecalculated using Colby's formula.

[0417] In this test, for example, the following active compoundcombination according to the present application exhibits asynergistically enhanced activity compared to the active compoundsapplied individually: TABLE A Sheet 1 Plant-damaging insects Aphisgossypii test Active compound Kill rate in % Active compoundsconcentration in ppm after 6^(d) Ex. I-10 1.6  0 Known Ex. II-a 1.6 25known Ex. I-10 + Ex. II-a (1:1) 1.6 + 1.6 found* Calc.** according tothe invention 95 25

[0418] TABLE A Sheet 2 Plant-damaging insects Aphis gossypii test Activecompound Kill rate in % Active compounds concentration in ppm after1^(d) Ex. I-10 8  0 known Ex. II-g 8 70 known Ex. I-10 + Ex. II-g (1:1)8 + 8 found* calc.** according to the invention 95 70

EXAMPLE B

[0419] Myzus Test

[0420] Solvent: 3 parts by weight of dimethylformamide

[0421] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0422] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted with water to the desiredconcentrations.

[0423] Cabbage leaves (Brassica oleracea) which are heavily infested bythe peach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

[0424] After the desired period of time, the kill in % is determined.100% means that all animals have been killed; 0% means that none of theanimals have been killed. The kill rates determined are calculated usingColby's formula.

[0425] In this test, for example, the following active compoundcombination according to the present application exhibits asynergistically enhanced activity compared to the active compoundsapplied individually: TABLE B Sheet 1 Plant-damaging insects Myzus testActive compound Kill rate in % Active compounds concentration in ppmafter 6^(d) Ex. I-10 1.6  5 known Ex. II-k 1.6 10 known Ex. I-10 + Ex.II-k (1:1) 1.6 + 1.6 found* Calc.** according to the invention 80 14.5

[0426] TABLE B Sheet 2 Plant-damaging insects Myzus test Active compoundKill rate in % Active compounds concentration in ppm after 6^(d) Ex.I-10 1.6  0 known Ex. II-g 1.6 10 known Ex. I-10 + Ex. II-g (1:1) 1.6 +1.6 found* Calc.** according to the invention 95 10

[0427] TABLE B Sheet 3 Plant-damaging insects Myzus test Active compoundKill rate in % Active compounds concentration in ppm after 1^(d) Ex.I-10 1.6  0 known Ex. II-m 1.6 15 known Ex. I-10 + Ex. II-m (1:1) 1.6 +1.6 found* calc.** according to the invention 45 15

EXAMPLE C

[0428] Critical Concentration Test/Soil Insects—Treatment of TransgenicPlants

[0429] Test insect: Diabrotica balteata—larvae in soil

[0430] Solvent: 7 parts by weight of acetone

[0431] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0432] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent,the stated amount of emulsifier is added and the concentrate is dilutedwith water to the desired concentration.

[0433] The preparation of active compound is poured on to the soil.Here, the concentration of active compound in the preparation isvirtually irrelevant, only the amount by weight of active compound pervolume unit of soil, which is stated in ppm (mg/l), matters. The soil isfilled into 0.25 l pots and these are allowed to stand at 20° C.

[0434] Immediately after preparation, 5 pre-germinated maize corns ofthe variety YIELD GUARD (trade mark of Monsanto Comp., USA) are placedinto each pot. After 2 days, the test insects are placed into thetreated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the maize plants that have emerged (1plant=20% efficacy).

EXAMPLE D

[0435] Heliothis Virescens Test—Treatment of Transgenic Plants

[0436] Solvent: 7 parts by weight of acetone

[0437] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0438] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0439] Soya bean shoots (Glycine max) of the variety Roundup Ready(trade mark of Monsanto Comp. USA) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with the tobacco budworm Heliothis virescens while the leavesare still moist.

[0440] After the desired period of time, the kill of the insects isdetermined.

What is claimed is: 1-9. (canceled)
 10. A composition comprising asynergistically effective mixture of (a) a compound of the formula (I)

in which X represents halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy, or cyano, W, Y, and Z independently of one another eachrepresent hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy, or cyano, A represents hydrogen, optionallyhalogen-substituted alkyl, alkoxyalkyl, or saturated optionallysubstituted cycloalkyl in which optionally one or more ring atoms arereplaced by a heteroatom, B represents hydrogen or alkyl, or A and Btogether with the carbon atom to which they are attached represent asaturated or unsaturated unsubstituted or substituted cycle thatoptionally contains one or more heteroatoms, D represents hydrogen or anoptionally substituted radical selected from the group consisting ofalkyl, alkenyl, alkoxyalkyl, and saturated cycloalkyl in whichoptionally one or more ring members are replaced by heteroatoms, or Aand D together with the atoms to which they are attached represent asaturated or unsaturated cycle that is unsubstituted or substituted inthe A-D moiety and optionally contains one or more heteroatoms, Grepresents hydrogen (a) or represents one of the groups

in which E represents a metal ion or an ammonium ion, L representsoxygen or sulphur, M represents oxygen or sulphur, R¹ represents in eachcase optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,alkylthioalkyl, or polyalkoxyalkyl; optionally halogen-, alkyl-, oralkoxy-substituted cycloalkyl that is optionally interrupted by one ormore heteroatoms; or in each case optionally substituted phenyl,phenylalkyl, hetaryl, phenoxyalkyl, or hetaryloxyalkyl, R² represents ineach case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, orpolyalkoxyalkyl or in each case optionally substituted cycloalkyl,phenyl, or benzyl, R³ represents optionally halogen-substituted alkyl oroptionally substituted phenyl, R⁴ and R⁵ independently of one anothereach represent in each case optionally halogen-substituted alkyl,alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, orcycloalkylthio or represent in each case optionally substituted phenyl,benzyl, phenoxy, or phenylthio, and R⁶ and R⁷ independently of oneanother each represent hydrogen, represent in each case optionallyhalogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, or alkoxyalkyl,represent optionally substituted phenyl, or represent optionallysubstituted benzyl or R⁶ and R⁷ together with the N atom to which theyare attached represent an optionally substituted ring that is optionallyinterrupted by oxygen or sulphur, and (b) at least one agonist orantagonist of nicotinic acetylcholine receptors selected from the groupconsisting of


11. A composition according to claim 10, wherein for a compound of theformula (I), W represents hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, chlorine,bromine, or fluorine, X represents C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-halogenoalkyl, fluorine, chlorine, or bromine, Y and Zindependently of one another each represent hydrogen, C₁-C₄-alkyl,halogen, C₁-C₄-alkoxy, or C₁-C₄-halogenoalkyl, A represents hydrogen orin each case optionally halogen-substituted C₁-C₆-alkyl orC₃-C₈-cycloalkyl, B represents hydrogen, methyl, or ethyl, or A and Btogether with the carbon atom to which they are attached representsaturated C₃-C₆-cycloalkyl in which optionally one ring member isreplaced by oxygen or sulphur and that is optionally mono- ordisubstituted by C₁-C₄-alkyl, trifluoromethyl or C₁-C₄-alkoxy, Drepresents hydrogen, in each case optionally fluorine- orchlorine-substituted C₁-C₆-alkyl, C₃-C₄-alkenyl, or C₃-C₆-cycloalkyl, orA and D together represent in each case optionally methyl-substitutedC₃-C₄-alkanediyl in which optionally one methylene group is replaced bysulphur, G represents hydrogen (a) or represents one of the groups

in which E represents a metal ion or an ammonium ion, L representsoxygen or sulphur, M represents oxygen or sulphur, R¹ represents in eachcase optionally halogen-substituted C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl,C₁-C₄-alkoxy-C₁-C₄-alkyl, or C₁-C₄-alkylthio-C₁-C₄-alkyl, or optionallyfluorine-, chlorine-, C₁-C₄-alkyl-, or C₁-C₂-alkoxy-substitutedC₃-C₆-cycloalkyl; represents optionally fluorine-, chlorine-, bromine-,cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl-, ortrifluoromethoxy-substituted phenyl; or represents in each caseoptionally chlorine- or methyl-substituted pyridyl or thienyl, R²represents in each case optionally fluorine- or chlorine-substitutedC₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, or C₁-C₄-alkoxy-C₂-C₄-alkyl; representsoptionally methyl- or methoxy-substituted C₅-C₆-cycloalkyl; orrepresents in each case optionally fluorine-, chlorine-, bromine-,cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl-, ortrifluoromethoxy-substituted phenyl or benzyl, R³ represents optionallyfluorine-substituted C₁-C₄-alkyl or represents optionally fluorine-,chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl-,trifluoromethoxy-, cyano-, or nitro-substituted phenyl, R⁴ represents ineach case optionally fluorine- or chlorine-substituted C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylamino, or C₁-C₄-alkylthio or represents in eachcase optionally fluorine-, chlorine-, bromine-, nitro-, cyano-,C₁-C₄-alkoxy-, trifluoromethoxy-, C₁-C₄-alkylthio-,C₁-C₄-halogenoalkylthio-, C₁-C₄-alkyl-, or trifluoromethyl-substitutedphenyl, phenoxy, or phenylthio, R⁵ represents C₁-C₄-alkoxy orC₁-C₄-thioalkyl, R⁶ represents C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₁-C₆-alkoxy, C₃-C₆-alkenyl, or C₁-C₄-alkoxy-C₁-C₄-alkyl, and R⁷represents C₁-C₆-alkyl, C₃-C₆-alkenyl or C₁-C₄-alkoxy-C₁-C₄-alkyl, or R⁶and R⁷ together represent an optionally methyl- or ethyl-substitutedC₃-C₆-alkylene radical in which optionally one carbon atom is replacedby oxygen or sulphur.
 12. A composition according to claim 10, whereinfor a compound of the formula (I), W represents hydrogen, methyl, ethyl,chlorine, bromine, or methoxy, X represents chlorine, bromine, methyl,ethyl, propyl, i-propyl, methoxy, ethoxy, or trifluoromethyl, Y and Zindependently of one another each represent hydrogen, fluorine,chlorine, bromine, methyl, ethyl, propyl, i-propyl, trifluoromethyl, ormethoxy, A represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl,sec-butyl, tert-butyl, cyclopropyl, cyclopentyl, or cyclohexyl, Brepresents hydrogen, methyl or ethyl, or A and B together with thecarbon atom to which they are attached represent saturated C₆-cycloalkylin which optionally one ring member is replaced by oxygen and that isoptionally monosubstituted by methyl, ethyl, methoxy, ethoxy, propoxy,or butoxy, D represents hydrogen, methyl, ethyl, propyl, i-propyl,butyl, i-butyl, allyl, cyclopropyl, cyclopentyl, or cyclohexyl, or A andD together represent optionally methyl-substituted C₃-C₄-alkanediyl, andG represents hydrogen (a) or represents one of the groups

in which M represents oxygen or sulphur, R¹ represents C₁-C₈-alkyl,C₂-C₄-alkenyl, methoxymethyl, ethoxymethyl, ethylthiomethyl,cyclopropyl, cyclopentyl, or cyclohexyl, represents optionallyfluorine-, chlorine-, bromine-, cyano-, nitro-, methyl-, ethyl-,methoxy-, trifluoromethyl-, or trifluoromethoxy-substituted phenyl, orrepresents in each case optionally chlorine- or methyl-substitutedpyridyl or thienyl, R² represents C₁-C₈-alkyl, C₂-C₄-alkenyl,methoxyethyl, or ethoxyethyl or represents phenyl or benzyl, and R⁶ andR⁷ independently of one another each represent methyl or ethyl, or R⁶and R⁷ together with the nitrogen to which they are attached represent


13. A composition according to claim 10, wherein for a compound of theformula (I), W represents hydrogen or methyl, X represents chlorine,bromine, or methyl, Y and Z independently of one another each representhydrogen, chlorine, bromine, or methyl, A and B together with the carbonatom to which they are attached represent saturated C₆-cycloalkyl inwhich optionally one ring member is replaced by oxygen and that isoptionally monosubstituted by methyl, methoxy, ethoxy, propoxy, orbutoxy, D represents hydrogen, G represents hydrogen (a) or representsone of the groups

in which M represents oxygen or sulphur, R¹ represents C₁-C₈-alkyl,C₂-C₄-alkenyl, methoxymethyl, ethoxymethyl, ethylmethylthio,cyclopropyl, cyclopentyl, or cyclohexyl, represents optionallyfluorine-, chlorine-, bromine-, methyl-, methoxy-, trifluoro-methyl-,trifluoromethoxy-, cyano-, or nitro-substituted phenyl, or represents ineach case optionally chlorine- or methyl-substituted pyridyl or thienyl,R² represents C₁-C₈-alkyl, C₂-C₄-alkenyl, methoxyethyl, ethoxyethyl,phenyl, or benzyl, R⁶ and R⁷ independently of one another each representmethyl or ethyl, or R⁶ and R⁷ together with the nitrogen to which theyare attached represent


14. A composition according to claim 10, wherein for a compound of theformula (I),

(1) W is H, X is Br, Y is 5-CH₃, Z is H, R is OCH₃, and G is CO-i-C₃H₇;(2) W is H, X is Br, Y is 5-CH₃, Z is H, R is OCH₃, and G is CO₂—C₂H₅;(3) W is H, X is CH₃, Y is 5-CH₃, Z is H, R is OCH₃, and G is H; (4) Wis H, X is CH₃, Y is 5-CH₃, Z is H, R is OCH₃, and G is CO₂—C₂H₅; (5) Wis CH₃, X is CH₃, Y is 3-Br, Z is H, R is OCH₃, and G is H; (6) W isCH₃, X is CH₃, Y is 3-Cl, Z is H, R is OCH₃, and G is H; (7) W is H, Xis Br, Y is 4-CH₃, Z is 5-CH₃, R is OCH₃, and G is CO-i-C₃H₇; (8) W isH, X is CH₃, Y is 4-Cl, Z is 5-CH₃, R is OCH₃, and G is CO₂—C₂H₅; (9) Wis H, X is CH₃, Y is 4-CH₃, Z is 5-CH₃, R is OCH₃, and G is

(10) W is CH₃, X is CH₃, Y is 3-CH₃, Z is 4-CH₃, R is OCH₃, and G is H;(11) W is H, X is CH₃, Y is 5-CH₃, Z is H, R is OC₂H₅, and G is

(12) W is CH₃, X is CH₃, Y is 3-Br, Z is H, R is OC₂H₅, and G isCO-i-C₃H₇; (13) W is H, X is CH₃, Y is 4-CH₃, Z is 5-CH₃, R is OC₂H₅,and G is CO-n-Pr; (14) W is H, X is CH₃, Y is 4-CH₃, Z is 5-CH₃, R isOC₂H₅, and G is CO-i-Pr; or (15) W is H, X is CH₃, Y is 4-CH₃, Z is5-CH₃, R is OC₂H₅, and G is CO-c-Pr.
 15. A composition according toclaim 10 comprising a compound of the formula (I) and the agonist orantagonist of nicotinic acetylcholine receptors of component (b) in aparts-by-weight ratio of from 1:100 to 100:1.
 16. A method ofcontrolling animal pests comprising exposing the animal pests to asynergistically effective mixture comprising the composition accordingto claim
 10. 17. A process for preparing pesticides comprising mixing asynergistically effective mixture comprising the composition accordingto claim 10 with extenders and/or surfactants.